Substituted 5-cycloalkyl-2,2-di-methyl-pentan-3-ones

ABSTRACT

Novel substitued 5-cycloalkyl-2,2-dimethyl-pentan-3-ones of the formula ##STR1## in which R is optionally substituted cycloalkyl, 
     X is halogen and 
     Y is hydrogen or halogen. 
     The new compounds are valuable intermediates for the synthesis of substances having plant growth-regulating and fungicidal properties.

The present invention relates to new substituted5-cycloalkyl-2,2-dimethyl-pentan-3-ones. The novel compounds arevaluable intermediates for the synthesis of substances having plantgrowth-regulating and fungicidal activity.

It has already been disclosed that azolyl-methylketones can be used asintermediates for the preparation of azolyl derivatives having plantgrowth-regulating and fungicidal properties (compare European PatentSpecification No. 0,032,200 and European Patent Specification No.0,031,911). Thus, for example,1-cyclohexyl-2-(1,2,4-triazol-1-yl)-4,4-bis-fluoromethyl-pentan-3-onecan be synthesised by reacting1-(1,2,4-triazol-1-yl)-3,3-bis-fluoromethyl-butan-2-one withcyclohexyl-methyl bromide according to the following equation: ##STR2##

The disadvantage is, however, that in this type of preparation of azolylderivatives having a plant growth-regulating and fungicidal activity,the azolyl-methylketones required as intermediates can be obtained onlyby multi-stage syntheses, and some of the materials thereby employed asstarting substances are accessible only with difficulty.

The present invention now provides, as new compounds, the substituted5-cycloalkyl-2,2-dimethyl-pentan-3-ones of the formula ##STR3## in which

R represents optionally substituted cycloalkyl,

X represents halogen and

Y represents hydrogen or halogen.

The new substances of the formula (I) are obtained by a process, whichcomprises reacting selectively a ketone of the formula ##STR4## in which

X and Y have the abovementioned meanings,

R¹ represents optionally substituted cycloalkyl, optionally substitutedcycloalkenyl or optionally substituted aryl and

R² represents optionally substituted aryl,

with hydrogen in the presence of a hydrogenation catalyst and, ifappropriate, in the presence of a diluent.

It has also been found that the new substituted5-cycloalkyl-2,2-dimethyl-pentan-3-ones of the formula (I) areparticularly suitable as intermediates for the preparation of4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones and -ols having a plantgrowth-regulating and fungicidal activity.

Surprisingly, 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones and -olshaving a plant growth-regulating and fungicidal action can be preparedfrom the substituted 5-cycloalkyl-2,2-dimethyl-pentan-3-ones of theformula (I) according to the invention more simply and in a higher yieldthan by the process known hitherto, in which the corresponding4-azolyl-2,2-dimethyl-butan-3-ones have been used as intermediates.

Formula (I) provides a general definition of the substances according tothe invention. Preferably, in this formula,

R represents cycloalkyl which has 5 to 7 carbon atoms and is optionallymono-, di- or tri-substituted by identical or different alkyl radicalswith 1 to 3 carbon atoms,

X represents fluorine or chlorine and

Y represents hydrogen, fluorine or chlorine.

Particularly preferred compounds of the formula (I) are those in which

R represents cyclohexyl which is optionally substituted by methyl;

X represents fluorine and

Y represents hydrogen or fluorine.

If, for example, 2,2-bisfluoromethyl-5-phenyl-pent-4-en-3-one andhydrogen are used as the starting substances and palladium andruthenium-on-active charcoal are used as catalysts, the course of thereaction in the process according to the invention can be represented bythe following equation: ##STR5##

If, for example, 2,2-bisfluoromethyl-5-(cyclohexen-1-yl)-pent-4-in-3-oneand hydrogen are used as starting substances and Raney nickel is used asthe catalyst, the course of the reaction in the process according to theinvention can be represented by the following equation: ##STR6##

If, for example, 2,2-bisfluoromethyl-5-phenyl-pentan-5-one and hydrogenare used as starting substances and ruthenium-on-active charcoal is usedas the catalyst, the course of the reaction in the process according tothe invention can be represented by the following equation: ##STR7##

The formula (IIa), (IIb) and (IIc) provide general definitions of theketones to be used as starting substances for carrying out the processaccording to the invention. In these formulae, R¹ preferably representscycloalkyl with 5 to 7 carbon atoms, cycloalkenyl with 5 to 7 carbonatoms or phenyl, in each case optionally mono-, di- or tri-substitutedby identical or different alkyl radicals with 1 to 3 carbon atoms. R²preferably represents phenyl which is optionally mono-, di- ortri-substituted by identical or different alkyl radicals with 1 to 3carbon atoms.

The ketones of the formula (IIa) are not yet known. Thus, the presentinvention also provides, as new compounds, the ketones of the formula(IIa).

The ketones of the formula (IIa) are obtained by a process, whichcomprises reacting a butan-2-one of the formula ##STR8## in which

X and Y have the abovementioned meanings, with an aldehyde of theformula

    R.sup.1 --CH═O                                         (IV)

in which

R¹ has the abovementioned meanings, in the presence of a diluent, suchas, for example, an alcohol, and in the presence of a base, such as, forexample, an alkali metal hydroxide or carbonate, at temperatures between10° C. and 80° C.

The butan-2-ones of the formula (III) and the aldehydes of the formula(IV) are known compounds of organic chemistry.

Further, the ketones of the formula (IIb) are not yet known. Saidketones of the formula (IIb) are the subject matter of a separatecopending patent application.

The ketones of the formula (IIb) are obtained by a process, whichcomprises reacting an acetylene derivative of the formula

    R.sup.1 --C.tbd.C--H                                       (V)

in which

R¹ has the abovementioned meanings, with a pivalic acid halide of theformula ##STR9## in which

X and Y have the abovementioned meanings and

Hal represents halogen, preferably chlorine or bromine, in the presenceof Cu-(I)-ions as the catalyst, and in the presence of a diluent, suchas, for example, toluene or pyridine, and in the presence of a base,such as, for example, triethylamine, at temperatures between 20° C. and100° C.

The acetylene derivatives of the formula (V) and the pivalic acidhalides of the formula (VI) are known compounds of organic chemistry.

The ketones of the formula (IIc) are also not yet known. Thus, thepresent invention also provides, as new compounds, the ketones of theformula (IIc).

The ketones of the formula (IIc) are obtained by a process, whichcomprises selectively hydrogenating the double bond or triple bond of aketone of the formula ##STR10## in which

R², X and Y have the abovementioned meanings,

with hydrogen in the presence of a diluent, such as, for example,methanol, and in the presence of a catalyst, such as, for example, Raneynickel or palladium-on-charcoal, under normal pressure or underincreased pressure, such as, preferably, 30 to 40 bar, at temperaturesbetween 20° C. and 40° C.

The process according to the invention is carried out in the liquidphase, preferably in the presence of diluents, using a suspended,pulverulent hydrogenation catalyst. The hydrogenation according to theinvention can be carried out discontinuously (batchwise) or continuouslyas liquid phase or trickle phase hydrogenation in known hydrogenationreactors, such as autoclaves, autoclave cascades, tube reactors orcirculatory reactors. The preferred procedure is discontinuous liquidphase hydrogenation in an autoclave under increased pressure.

Possible diluents in carrying out the process according to the inventionare inert organic solvents. These include, preferably, alcohols, such asmethanol, ethanol, isopropanol or ethylene glycol; ethers, such asdiethyl ether, diisopropyl ether, ethylene glycol monomethyl ether,ethylene glycol dimethyl ether, dioxane or tetrahydrofuran; saturatedhydrocarbons, such as n-heptane or cyclohexane; and esters, such asethyl acetate.

Examples of suitable hydrogenation catalysts for the process accordingto the invention are those which consist of or contain metals and/orcompounds of subgroup 8 of the Mendeleev periodic table of the elements.The metal ruthenium, rhodium, palladium, platinum, cobalt and nickel andcompounds thereof are preferred here. The metal compounds can be, forexample, oxides, hydroxides and/or hydrated oxides. In addition, themetals copper, vanadium, molybdenum, chromium and/or magnanese andcompounds of these metals can be present.

The hydrogenation catalysts can consist exclusively or predominantly ofsubstances which transfer hydrogen, but these can also be applied tosupports.

Examples of possible supports for the substances which transfer hydrogenare: inorganic materials, such as kieselguhr, salicic acid, aluminiumoxide, alkali metal and alkaline earth metal silicates, aluminiumsilicates, montomorillonite, zeolites, spinels, dolomite, kaolin,magnesium silicates, zirconium oxide, zinc oxide, calcium carbonate,silicon carbide, aluminium phosphate, boron phosphate, asbestos, activecharcoal or barium sulphate, and also organic materials, for examplenaturally occurring or synthetic compounds with high molecular weights,such as silk, polyamides, polystyrenes, cellulose or polyurethanes.Inorganic supports in powder form are preferred.

Such supported catalysts can in general contain 0.5 to 50% by weight,preferably 1 to 10% by weight, of the substance which transfershydrogen, based on the total weight of the supported catalyst. Thesubstance which transfers hydrogen can thereby be homogeneouslydistributed in the support, but catalysts containing a deposit of thesubstance which transfers hydrogen in their outer layer or on theirsurfaces are preferred. The catalysts which can be used in the processaccording to the invention can be prepared and shaped in a known manner(see, for example, Houben-Weyl, Methoden der organischen Chemie (Methodsof Organic Chemistry), Volume 4, Ic, Part I, pages 16 to 26, GeorgThieme Verlag, Stuttgart, 1980).

Preferred supported catalysts are ruthenium-on-charcoal,ruthenium-on-aluminium oxide, rhodium-on-charcoal, rhodium-on-aluminiumoxide, palladium-on-charcoal, palladium-on-aluminium oxide,palladium-on-calcium carbonate, palladium-on-barium sulphate,palladium-on-salicic acid, platinum-on-charcoal andplatinum-on-aluminium oxide, nickel-on-kieselguhr, nickel-on-aluminiumoxide and nickel and palladium-on-aluminium oxide.

Examples of preferred hydrogenation catalysts which consist exclusivelyor predominantly of the substance which transfers hydrogen are oxidiccatalysts, such as palladium oxide, platinum oxide, ruthenium oxideand/or rhodium oxide/platinum according to Nishimura, and furthermoreblack catalysts which can be prepared by production of correspondingmetal salts or metal salt mixtures with alkali metal hydrides, alkalimetal boronates, metal-alkyls, hydrazine, formaldehyde, hydrogen or moreelectropositive metals, such as palladium black, platinum black andrhodium black; and skeleton catalysts of the Raney type, such as Raneynickel, Raney cobalt, Raney nickel/cobalt, Raney nickel/iron, Raneynickel/copper, Raney nickel/iron/chromium, Raney nickel/palladium andRaney nickel/iron/vanadium.

The selection of one or more of the hydrogenation catalysts mentionedadvantageously depends on the structure of the starting ketones of theformulae (IIa), (IIb) and (IIc) to be hydrogenated according to theinvention.

If the ketones of the formulae (IIa) and (IIb) contain optionallysubstituted cycloalkenyl radicals or optionally substituted cycloalkylradicals as the substituent R¹, those catalysts which contain or consistof nickel and/or palladium are particularly preferred for conversionthereof into saturated ketones of the formula (I). If the ketones of theformulae (IIa) and (IIb) contain optionally substituted aryl radicals asthe substituent R¹ or if a ketone of the formula (IIc) is concerned,those catalysts which contain or consist of ruthenium, rhodium and/orplatinum are particularly preferred for conversion thereof intosaturated ketones of the formula (I).

The hydrogenation catalysts are used in the process according to theinvention in an amount such that 0.05 to 2.5% by weight, preferably 0.1to 1% by weight, of the substance which transfers hydrogen is present,based on the total weight of the reaction mixture.

Mixtures of two or more of the hydrogenation catalysts mentioned canalso be used for carrying out the process according to the invention.

The catalytic activity of the hydrogenation catalysts is in generalsubstantially retained in carrying out the process according to theinvention, so that these can be used repeatedly in the case of adiscontinuous procedure, and can remain in use for a relatively longtime in the case of the continuous procedure.

The reaction temperatures can be varied within a substantial range. Ingeneral, the reaction is carried out in the range between 0° C. and 150°C., preferably between 20° C. and 120° C. Reaction temperatures in therange from 20° C. to 60° C. are particularly preferred for thehydrogenation of aliphatic and/or cycloaliphatic C--C multiple bonds inthe ketones of the formulae (IIa) and (IIb) with the catalysts preferredfor this hydrogenation, whilst temperatures in the range from 60° C. to120° C. are particularly preferred for the hydrogenation of arylradicals in the ketones of the formulae (IIa), (IIb) and (IIc) with thecatalysts preferred for this hydrogenation.

The hydrogenation reactions according to the invention are preferablycarried out under increased pressure. In general, the hydrogenation iscarried out between 1 and 150 bar, preferably under 20 to 120 bar.Pressures in the range from 5 to 50 bar are particularly preferred forthe hydrogenation of aliphatic and/or cycloaliphatic C--C multiple bondsin the ketones of the formulae (IIa) and (IIb) with the catalystspreferred for this hydrogenation, whilst pressures in the range from 5to 120 bar are particularly preferred for the hydrogenation of arylradicals in the ketones of the formulae (IIa), (IIb) and (IIc) with thecatalysts preferred for this hydrogenation.

The reaction time required for the process according to the inventiondepends on the reaction temperature, the partial pressure of hydrogen,the intensity of mixing of the reaction mixture and the activity andconcentration of the hydrogenation catalyst. In general, the reactiontime necessary is in the range from 15 minutes to several hours.

In the simplest embodiment, the process according to the invention canbe carried out, for example, discontinuously in the following manner: anautoclave which can be temperature-controlled and is provided with astirring or mixing device is charged in a suitable manner with a ketoneof the formula (IIa), (IIb) or (IIc), the hydrogenation catalyst and thediluent. After the air has been removed from the autoclave and hydrogenhas been forced in up to the desired pressure, the mixture is heated tothe chosen reaction temperature, with intensive mixing. The course ofthe reaction can easily be monitored by measuring the hydrogenconsumption, which is compensated by feeding in further hydrogen. Thehydrogenation has ended when no further hydrogen is consumed and theamount of hydrogen consumed approximately corresponds to thetheoretically required amount of hydrogen.

When the hydrogenation has ended, the reaction mixture is cooled, letdown, and worked up in a known manner, for example by removing thecatalyst by filtration and distilling off the diluent.

In a particular embodiment of the reaction according to the invention, aprocedure is followed in which ketones of the formula (IIa) which carryan optionally substituted aryl radical as the substituent R¹ arehydrogenated to the corresponding ketones of the formula (IIc) in afirst stage, and these ketones are then hydrogenated to the end productsof the formula (I) in a second stage (compare also the preparationexamples). It should be emphasised that only the C--C multiple bonds arehydrogenated, with a high selectivity, whilst the CO double bond isretained.

As already mentioned, the new 5-cycloalkyl-2,2-dimethyl-pentan-3-ones ofthe formula (I) are useful intermediates for the synthesis of4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones and -ols havingfungicidal and plant growth-regulating properties.

Such 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones and -ols of theformula (VII) ##STR11## in which

R, X and Y have the abovementioned meanings and

A represents a keto group or the CH(OH) group, can be prepared by aprocess in which 5-cycloalkyl-2,2-dimethyl-pentan-3-ones of the formula(I) ##STR12## in which

R, X and Y have the abovementioned meanings, are reacted with chlorineor bromine in the presence of an inert organic solvent, such as, forexample, ether or chlorinated or non-chlorinated hydrocarbons, at roomtemperature, or are reacted with customary chlorinating agents, such as,for example, sulphuryl chloride, at 20° C. to 60° C.; thehalogenoketones thus obtained, of the formula (VIII) ##STR13##

R, X and Y have the abovementioned meanings and

Z represents chlorine or bromine, are then reacted with 1,2,4-triazolein the presence of an inert organic solvent, such as, for example,acetonitrile, and in the presence of an acid-binding agent, such as, forexample, potassium carbonate, or in the presence of an excess of1,2,4-triazole, at temperatures between 60° C. and 120° C.; and, ifappropriate, the 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones thusobtained, of the formula (VIIa) ##STR14## in which

R, X and Y have the abovementioned meanings, are subsequently reduced byreaction with complex hydrides, such as sodium borohydride or lithiumalanate, in the presence of a polar organic solvent, such as, forexample, an alcohol, at temperatures between 0° C. and 30° C.; or arereduced by reaction with aluminium isopropylate in the presence of adiluent, such as, for example, isopropanol, at temperatures from 20° C.to 120° C.

The 4-azolyl-5-cycloalkyl-2,2-dimethyl-pentan-3-ones and -ols of theformula (VII) have powerful fungicidal and plant growth-regulatingproperties (compare European Pat. No. 0,031,911 and European Pat. No.0,032,200).

The preparation and use of the substances according to the invention canbe seen from the following examples.

PREPARATION EXAMPLES EXAMPLE 1 ##STR15## Process variant 1

1st stage: ##STR16##

A 120 liter stainless steel stirred autoclave which can betemperature-controlled with the aid of an adjustable thermostat wascharged with 30 kg (133.9 mol) of2,2-bisfluoromethyl-5-phenyl-pent-4-en-3-one, 60 liters of methanol and0.6 kg of Raney nickel.

After the autoclave had been closed and the air had been displaced withnitrogen the mixture employed was charged with hydrogen up to a pressureof 30 bar and was then heated to 80° C., with stirring. As soon as thistemperature had been reached, the hydrogen pressure was increased to 40bar and was maintained at this level in accordance with the rate ofconsumption of the hydrogen throughout the entire reaction time.

When the uptake of hydrogen had ended, after about 5 hours, stirring wascontinued under the abovementioned hydrogenation conditions for afurther hour in order to bring the reaction to completion, and themixture was then cooled to room temperature and let down to normalpressure.

The product solution separated off from the catalyst by filtration wasfurther reacted directly in the second stage without being isolated. Theresulting 2,2-bisfluoromethyl-5-phenyl-pentan-3-one had a content of 98%(determined by gas chromatography).

2nd stage: ##STR17##

A 120 liter stainless steel stirred autoclave which can betemperature-controlled with the aid of an adjustable thermostat wascharged with a solution of 29.7 kg (131.4 mol) of2,2-bisfluoromethyl-5-phenyl-pentan-3-one in 60 liters of methanol and0.72 kg of a catalyst containing 5% of ruthenium-on-active charcoal.

After the autoclave had been closed and the air had been displaced withnitrogen, the mixture employed was charged with hydrogen up to apressure of 50 bar and was heated to 90° C., with stirring. As soon asthis temperature had been reached, the hydrogen pressure was increasedto 100 bar and was maintained at this level in accordance with the rateof consumption of the hydrogen throughout the entire reaction time.

When the uptake of hydrogen had ended, after about 6 hours, stirring wascontinued under the abovementioned hydrogenation conditions for afurther hour in order to bring the reaction to completion, and themixture was then cooled to room temperature and let down to normalpressure.

The product solution separated off from the catalyst by filtration wasfreed from the methanol in a rotary evaporator.

30.3 kg (99.4% of theory) of2,2-bisfluoromethyl-5-cyclohexyl-pentan-3-one were obtained as an oilwith a content of 96% (determined by gas chromatography).

Preparation of the starting substance: ##STR18##

A mixture of 106.1 g (1 mol) of benzaldehyde, 136.1 g (1 mol) of3,3-bisfluoromethyl-butan-2-one, 300 g of methanol and 40 g (1 mol) ofsodium hydroxide in 70 g of water was stirred at room temperature for 3hours. The crystalline product was then filtered off and dried.

201.8 g (90% of theory) of 2,2-bisfluoromethyl-5-phenyl-pent-4-en-3-oneof melting point 45° C. were obtained.

EXAMPLE 2 ##STR19## Process variant 2

A 0.7 liter stainless steel stirred autoclave which can betemperature-controlled with the aid of an adjustable thermostat wascharged with 112 g (0.5 mol) of2,2-bisfluoromethyl-5-phenyl-pent-4-en-3-one, 300 ml of methanol, 2,8 gof a catalyst containing 5% of palladium-on-active charcoal and 2.8 g ofa catalyst containing 5% of ruthenium-on-active charcoal.

After the autoclave had been closed and the air had been displaced bynitrogen, hydrogen was passed in up to a pressure of 30 bar and themixture was heated to 40° C., with stirring. As soon as this temperaturewas reached, the hydrogen pressure was increased to 50 bar and wasmaintained at this level until the uptake of hydrogen subsided (H₂consumption about 0.5 mol in 1.5 hours). The reaction solution was thenincreased to 70° C. and the hydrogen pressure was increased to 100 bar,and the hydrogenation was continued under these conditions bycontinuously forcing more hydrogen up to a pressure of 100 bar inaccordance with the hydrogen consumption, which can be recognised by thedrop in pressure (H₂ consumption about 1.5 mol in 5 hours).

When the uptake of hydrogen had ended, the mixture was cooled to roomtemperature and let down to normal pressure. The product solutionseparated off from the catalyst by filtration was freed from themethanol in a rotary evaporator.

113 g (97.4% of theory) of 2,2-bisfluoromethyl-5-cyclohexyl-pentan-3-onewere obtained as an oil with a content of 89% (determined by gaschromatography).

EXAMPLE 3 ##STR20## Process variant 3

1st stage: ##STR21##

A 0.3 liter stainless steel stirred autoclave which can betemperature-controlled with the aid of an adjustable thermostat wascharged with 44.4 g (0.2 mol) of2,2-bisfluoromethyl-5-phenyl-pent-4-in-3-one, 170 ml of methanol and 5 gof Raney nickel.

After the autoclave had been closed and the air had been displaced withhydrogen, the mixture employed was charged with hydrogen up to apressure of 30 bar and was heated to 30° C., with stirring. As soon asthis temperature had been reached, the hydrogen pressure was increasedto 50 bar and was maintained at this level in accordance with the rateof consumption of the hydrogen throughout the entire reaction time.

When the uptake of hydrogen had ended, after about 2 hours, stirring wascontinued under the abovementioned hydrogenation conditions for afurther hour in order to bring the reaction to completion, and themixture was then cooled to room temperature and let down to normalpressure.

The product solution separated from the catalyst by filtration was freedfrom the methanol in a rotary evaporator.

44.5 g (98.5% of theory) of 2,2-bisfluoromethyl-5-phenyl-pentan-3-onewere obtained as an oil with a content of 96.5% (determined by gaschromatography).

2nd stage: ##STR22##

The reaction proceeds in the same way as the 2nd stage of processvariant 1.

Preparation of the starting substance ##STR23##

10.1 g (0.1 mol) of triethylamine and 1.43 g (0.01 mol) of copper-Ibromide were initially introduced into 30 ml of pyridine, undernitrogen. 10.2 g (0.1 mol) of phenylacetylene were added and the mixturewas subsequently stirred for 30 minutes. Thereafter, 15.6 g (0.1 mol) ofα,α-bisfluoromethyl-propionyl chloride were added dropwise to thereaction mixture, the temperature thereby being kept at 60° C. Themixture was stirred at this temperature for 15 hours, cooled, washedwith water, dried over sodium sulphate and concentrated in vacuo. Theresidue was purified by distillation.

17.3 g (78% of theory) of 2,2-bisfluoromethyl-5-phenyl-pent-4-in-3-oneof boiling point 103° C. to 105° C./0.2 mbar were obtained.

EXAMPLE 4 ##STR24## Process variant 4

A 0.3 liter stainless steel stirred autoclave which can betemperature-controlled with the aid of an adjustable thermostat wascharged with 24 g (0.106 mol) of2,2-bisfluoromethyl-5-(cyclohexen-1-yl)-pent-4-in-3-one, 120 ml ofmethanol and 5 g of Raney nickel.

After the autoclave had been closed and the air had been displaced withnitrogen, the mixture employed was charged with hydrogen up to apressure of 50 bar and was heated to 50° C., with stirring. As soon asthis temperature had been reached, the hydrogen pressure was increasedto 70 bar and was kept at this level in accordance with the rate ofconsumption of the hydrogen throughout the entire reaction time.

When the uptake of hydrogen had ended, stirring was continued under theabovementioned hydrogenation conditions for a further hour in order tobring the reaction to completion, and the mixture was then cooled toroom temperature and let down to normal pressure.

The product solution separated off from the catalyst by filtration wasfreed from the methanol on a rotary evaporator.

23.5 g (95.5% of theory) of2,2-bisfluoromethyl-5-cyclohexyl-pentan-3-one were obtained as an oilwith a content of 88.5% (determined by gas chromatography).

Preparation of the starting substance ##STR25##

10.1 g (0.1 mol) of triethylamine and 1.43 g (0.1 mol) of copper-Ibromide were initially introduced into 30 ml of pyridine under nitrogen.10.6 g (0.1 mol) of cyclohexen-1-yl-acetylene were added and the mixturewas subsequently stirred for 30 minutes. Thereafter, 15.6 g (0.1 mol) ofα,α-bis-fluoromethyl-pripionyl chloride were added dropwise to thereaction mixture and the temperature was kept at 70° C. The mixture wassubsequently stirred at this temperature for 15 hours, cooled, washedwith water, dried over sodium sulphate and concentrated in vacuo. Theresidue was purified by distillation.

18.1 g (80% of theory) of2,2-bisfluoromethyl-5-(cyclohexen-1-yl)-pent-4-in-3-one of boiling point106° C. to 109° C./0.3 mbar were obtained.

Preparation of 4-azolyl-5-cycloalkyl-2,2-dimethylpentan-3-ones of theformula (VII) EXAMPLE 5 ##STR26## 1st stage: ##STR27##

232.3 g (1 mol) of 2,2-bisfluoromethyl-5-cyclohexyl-pentan-3-one(Example 1) were heated to 80° C. and 161.9 g (1.2 mol) of sulphurylchloride were added dropwise in the course of 1 hour. The mixture wassubsequently stirred at 80° C. for 5 hours and excess sulphuryl chloridewas then distilled off in vacuo. After the mixture had been cooled to20° C., 500 ml of methyl isobutyl ketone were added. The organicsolution was washed neutral with water, dried over magnesium sulphateand concentrated in vacuo. The residue was distilled.

252 g (90% of theory) of2,2-bisfluoromethyl-5-chloro-5-cyclohexyl-pentan-3-one of boiling point118° C. to 120° C./2.5 mbar were obtained.

2nd stage: ##STR28##

266.7 g (1 mol) of2,2-bisfluoromethyl-4-chloro-5-cyclohexyl-pentan-3-one, 69.1 g (1 mol)of 1,2,4-triazole and 165.8 g (1.2 mol) of potassium carbonate in 1000ml of methyl isobutyl ketone were heated under reflux for 6 hours. Aftercooling, the mixture was washed with dilute hydrochloric acid and washedneutral with water. The organic phase was dried over magnesium sulphateand concentrated in vacuo.

329 g (88% of theory) of2,2-bisfluoromethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-pentan-3-one ofrefractive index n_(D) ²⁰ =1.4933 were obtained.

EXAMPLE 6 ##STR29##

299 g (1 mol) of2,2-bisfluoromethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-pentan-3-one(Example 5) were dissolved in 300 ml of methanol, and a solution of 13.2g (0.35 mol) of sodium borohydride in 150 ml of 0.1 normal aqueoussodium hydroxide solution was added dropwise at 0° C. to 5° C. After areaction time of 2 hours, the reaction solution was brought to a pHvalue of 4 to 5 with dilute aqueous hydrochloric acid. After addition of500 ml of water, the end product crystallised out.

After drying in vacuo, 286 g (95% of theory) of2,2-bisfluoromethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-pentan-3-ol ofmelting point 103° C. to 105° C. were obtained.

Comparison example

Preparation of the (1,2,4-triazol-1-yl) derivative of the formula##STR30## by the process known hitherto. 1st stage: ##STR31##

400 ml of tetraethylene glycol and 46.4 g of potassium fluoride (0.8mol) were initially introduced into a three-necked flask with a stirrer,dropping funnel and a Liebig condenser with a cooled receiver, and wereheated to 170° C. A water pump vacuum (pressure about 20 to 30 mbar) wasapplied to the adaptor of the Liebig condenser. 57.6 g (0.2 mol) of2-acetyl-2-methyl-propane-1,3-diol bismethanesulphate, dissolved in 100ml of tetraethylene glycol, were then added dropwise in the course of 45minutes. The 3,3-bisfluoromethyl-butan-2-one formed was distilled offinto the cooled receiver during the reaction. After the dropwiseaddition, the distillation was continued at 175° C. for a further hour.The distillate collected was then redistilled. 14 g (51.5% of theory) of3,3-bisfluoromethylbutan-2-one of boiling point 43° to 46° C./12 mbarwere obtained.

2nd stage: ##STR32##

51 ml (1 mol) of bromine were added dropwise to 136 g (1 mol) of3,3-bisfluoromethylbutan-2-one in 700 ml of methylene chloride such thatdecoloration was continuous. The solvent was then distilled off under awater pump vacuum. An almost quantitative yield of crude3,3-bisfluoromethyl-1-bromo-butan-2-one was obtained as an oil, whichcould be further reacted directly.

3rd stage: ##STR33##

215 g (1 mol) of crude 3,3-bisfluoromethyl-1-bromobutan-2-one were addeddropwise to 84 g (1.2 mol) of 1,2,4-triazole and 165 g (1.2 mol) ofground potassium carbonate in 1 liter of ethanol at 30° to 35° C. Themixture was subsequently stirred overnight at 40° C., the insolublematerial was then filtered off and the filtrate was concentrated. Theoily residue was extracted with methylene chloride and water and theextract was dried over sodium sulphate and concentrated. The residue wastaken up in methylene chloride, and 140 ml of ethereal hydrochloric acidwere added. The crystalline product formed was filtered off with suctionand extracted with 1 liter of methylene chloride and 1 liter ofsaturated aqueous sodium bicarbonate solution, and the extract waswashed with 1 liter of water, dried over sodium sulphate andconcentrated. 73.8 g (36.4% of theory) of3,3-bisfluoromethyl-1-(1,2,4-triazol-1-yl) were obtained as an oil,which could be further reacted directly.

4th stage: ##STR34##

A solution of 101.4 g (1.81 mol) of potassium hydroxide in 217.2 ml ofwater was added to a solution of 369.4 g (1.81 mol) of2,2-bisfluoromethyl-4-(1,2,4-triazol-1-yl)-butan-3-one in 2 liters ofdimethylsulphoxide at room temperature, with stirring. 320.5 g (1.81mol) of cyclohexylmethyl bromide were added dropwise to this mixture,with stirring, the temperature of the reaction mixture being keptbetween 20° and 40° C. by cooling. The reaction mixture was stirred at60° C. for a further 15 hours and then poured into 2 liters of water.The resulting mixture was extracted twice with 1 liter of methylenechloride each time, the combined organic phases were washed four timeswith 2 liters of water each time and dried over sodium sulphate and thesolvent was stripped off. The resulting oily product was taken up inacetone, and 326 g of naphthalene-1,5-disulphonic acid were added to thesolution. The precipitate which thereby formed was filtered off withsuction and suspended in 2 liters of methylene chloride. This suspensionwas shaken twice with 2 liters of saturated aqueous sodium bicarbonatesolution each time. The organic phase was then washed with 2 liters ofwater and, after drying over sodium sulphate, was concentrated underreduced pressure. 297.5 g (63% of theory) of2,2-bis-fluoromethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-pentan-3-onewere obtained in this manner in the form of an oil. n_(D) ²⁰ =1.4837.

It will be understood that the specification and examples areillustrative, but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

What is claimed is:
 1. A substituted5-cycloalkyl-2,2-dimethyl-pentan-3-one of the formula ##STR35## in whichR is cycloalkyl with 5 to 7 carbon atoms or cycloalkyl with 5 to 7carbon atoms which is mono-, di- or tri-substituted by identical ordifferent alkyl radicals with 1 to 3 carbon atoms,X is halogen and Y ishydrogen or halogen.
 2. A compound as claimed in claim 1, wherein X isfluorine or chlorine.
 3. A compound as claimed in claim 1, wherein Y ishydrogen, fluorine or chlorine.
 4. A compound as claimed in claim 1,whereinR is cyclohexyl or methyl substituted cyclohexyl, X is fluorineand Y is hydrogen or fluorine.
 5. A compound as claimed in claim 1,characterized by the formula ##STR36##